GB2046768A

GB2046768A - Coloured polymeric materials comprising copolymerized

Info

Publication number: GB2046768A
Application number: GB8005165A
Authority: GB
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1979-02-15
Filing date: 1980-02-15
Publication date: 1980-11-19
Also published as: GB2046768B; FR2450848A1; IT8019861A0; IT1193519B; FR2450848B1; CA1130804A; US4267306A; NL8000938A; DE3005223A1; JPS55112234A

Description

1

GB 2 046 768 A 1:

10

15

SPECIFICATION

Coloured polymeric materials comprising copolymerized dyes • .■

This invention relates to anthraquinone dyes that are copolymerized into linear saturated or unsaturated crosslinkable polyesters to impart colour to the polyesters. The dyes are thermally stable at polyester processing temperatures and they are colourfast and nonextractable from the polyesters. Polyesters containing these dyes can be used to mould beverage bottles.

Anthraquinone dyes have been used to dye polyesters, as in, for example, United States Patent Specification No. 3,689,501. The polyesters have been formed and then dyed with the anthraquinone dyes in a procedure that is separate from the polymerization process.

The present invention eliminates the need for a separate dyeing procedure to colour the polyesters: the anthraquinone dyes are copolymerized with the polyesters during the polymerization process.

In accordance with the present invention, there is provided coloured polymeric material comprising a linear thermoplastic or unsaturated cross-linkable polyester copolymerized with a colouring compound of the formula

10

15'

RH4.C2—-N- -N

hc. c-s-

V

N-C2H4R

or

20

NHCH2

(CH2R)n wherein R is —OH, —COOR1 or —COX wherein R1 is hydrogen or a lower alkyl radical, X is halogen, n is 1 or 2, A or B of II must contain, and A or B of I may contain, at least one additional .

—nhch2:

(ch2r)n

20

radical, each of rings A and B may be further substituted with 1—3 radicals selected from lower alkyl which may be substituted with lower alkoxy, phenyl, chlorine, bromine, and lower alkanoylamino; lower alkoxy which may be substituted with lower alkoxy, phenyl, chlorine, bromine, and lower alkanoylamino; chlorine, bromine; amino; lower alkylamino which may be substituted with lower alkoxy, cyclohexyl, 25 phenyl, chlorine, bromine, and lower alkanoylamino; arylamino; arylthio; and aroylamino; wherein each aryl is 6—10 carbons; lower alkylsulphonyl; lower alkylthio; lower alkanoylamino; and cyclohexylamino.

The term "lower" means that 1 to 6 carbon atoms are present.

Preferably X is chlorine or bromine.

Preferably each aryl is phenyl.

30 The dyes have excellent heat stability and resistance to fading by light. Brightly coloured polyesters can be obtained by copolymerization with one or more of the dyes, and the polyesters can be blown into bottles and/or moulded into many useful articles. Practically any colour can be obtained with the proper combination of blue, red, and yellow dyes of this type, and, if desired, other known pigments and/or fillers may be admixed with the polymers to give the effects needed.

35 The dyes of formula II can be prepared by reacting anthraquinone intermediates containing labile groups such as halogen, hydroxyl, nitro, sulphonic acid and phenoxy with an aminomethylcyclohexane methyl derivatives such as 2,3 or 4-aminomethylcyclohexane methanol or mixtures thereof, including mixtures .of cis and trans isomers. Examples 1 and 2 illustrate the preparation of dyes of formula II.

25

30

35

2

GB 2 046 768 A 2

EXAMPLE 1

Preparation of 1,5-Bis[[[4-(hydroxymethyl)cyclohexyl]-methyl]amino]anthraquinone

A mixture of 1,5-dichloroanthraquinone (77.6 g), trans-4-aminomethylcyclohexane methanol (180 g), ethylene glycol monomethyl ether (280 ml), and potassium carbonate (38.7 g) was stirred and 5 heated at reflux for eight hours. The mixture was cooled below 100°C. and hot water (350 ml) was .... 5 added. The dye was collected by filtering at 80°C. and washed with methanol and then water. The moist cake was slurried in ethylene glycol monomethyl ether (500 ml) and the mixture was heated to reflux. After cooling to room temperature, the dye was collected by filtration, washed with acetone, and finally with water. The yield of red dye was 110 g or about 80% of the theoretical yield.

10 EXAMPLE 2 10

Preparation of 1,4-Bis[[[4-(hydroxymethyl)cyclohexyl]methyl]amino]anthraquinone

A mixture of quinzarin (37.5 g) and leucoquinizarin (12.5 g) was added in portions over about one hour to trans-4-aminomethylcyclohexane methanol (200 g) at 125—1 30°C. The temperature was held at 125—130°C. for an additional-two hours and then the reaction mixture was added with stirring to a 15 2% aqueous sodium hydroxide solution (800 ml). Air and steam were blown through the mixture for one 15 hour and then the dye was collected by filtration and washed with water. The moist cake was slurried in isopropanol (250 ml) at 55—60°C. and the mixture was then filtered. The dye cake was washed with acetone and then dried in air. The yield was 78 g or 77% of the theoretical yield.

The following examples illustrate the dyeing of polyesters by copolymerizing the dyes of formula I 20 and II with the polyesters. The inherent viscosities were measured using 0.50 gram of polyester per 100 20 ml of a solvent composed of 60 volumes of phenol and 40 volumes of tetrachloroethane.

EXAMPLE 3

Preparation of Copolyester Containing Copolymerized Red Dye (The ppm is based on one million parts by weight of the total polymer)

25 145.5 g (0.75 mole) dimethyl terephthalate 25

89.0 g (1.44 mole) ethylene glycol 32.8 g (0.23 mole) 1,4-cyclohexanedimethanol 50 ppm Mn, 250 ppm Sb, 30 ppm Ti, 70 ppm P

100 ppm red dye, 1,5-bis[[[4-(hydroxymethyl)cyclohexyl[methyl]amino]anthraquinone 30 The above reactants, with the exception of phosphorus, were added to a 500-ml round bottom 30 flask fitted with a stirrer, condensate take-off, and nitrogen inlet head. The flask and contents were immersed in a metal bath at 170°C. The temperature was raised to 195°C. and maintained for two hours and 20 minutes while ester exchange of the dimethyl terephthalate, ethylene glycol, 1,4-cyclohexanedimethanol, and 1,5-bis[[[4-(hydroxymethyl)cyclohexyl]methyl]amino]anthraquinone took 35' place. The temperature was then raised to 215°C. and maintained for one hour and 30 minutes to 35

complete the ester exchange. The temperature was raised to 240°C. and the phosphorus was added. The temperature was then raised to 285°C. At 285°C., the melt was placed under 0.10 mm Hg vacuum and polymerization was continued for 45 minutes. The resulting polymer, obtained in essentially 100%

yield, was brilliant red and had an inherent viscosity of 0.706.

40 EXAMPLE 4 40

Preparation of Copolyester Containing Copolymerized Blue Dye

This composition was the same as in Example 3 except that 100 ppm of blue dye, 1,4-bis[[[4-(hydroxymethyl)cyclohexyl]methyl]amino]anthraquinone, was used. The ester exchange and polymerization conditions were the same as in Example 3 and the resulting polymer was dark blue and • 45 had an inherent viscosity of 0.742. 45

EXAMPLE 5

Preparation of Green Polyester

145.5 g (0.75 mole) dimethyl terephthalate 93.0 g (1.50 moles) ethylene glycol 50 120 ppm Ti catalyst

800 ppm yellow dye 1,5-bis[[1 -(2-hydroxyethyl)-1,2,4-triazol-3-yl]thio]anthraquinone 1 50 ppm phthalocyanine blue pigment

30 ppm red dye 1,5-bis[[[4-(hydroxymethylcyclohexyl]methyl]amino]anthraquinone The ester interchange and polymerization of this polymer were carried out as in Example 3. The 55 resulting polymer was "Emerald Green" and had an inherent viscosity of 0.661.

EXAMPLE 6

Preparation of Green Polyester

This example illustrates that the dye concentration shown in Example 3 can be reduced and essentially the same colour and density of colour obtained by the addition of iron oxide.

60 145.5 g (0.75 mole) dimethyl terephthalate 50

50

55

3

GB 2 046 768 A 3

93.0 g (1.50 moles) ethylene glycol 120 ppm Ti catalyst

400 ppm yellow dye, 1,5-bis[[1,(2-hydroxyethyl)-1,2,4-triazol-3-yl]thio]anthraquinone 100 ppm phthalocyanine blue pigment 5 15 ppm red dye, 1,5-bis[[[4-(hydroxymethyl)cyclohexyl]methyl]amino]anthraquinone

200 ppm iron oxide BK-45 (Hoechst)

The ester exchange and polymerization of this polymer were carried out as described in Example 3. The resulting polymer was "Emerald Green", similar to the polymer produced in Example 5, and had an inherent viscosity of 0.732.

10 EXAMPLE 7

Preparation of "Blue-White" Polyester

145.50 g (0.75 mole) dimethyl terephthalate 93.00 g (1.50 moles) ethylene glycol 50 ppm Mn, 250 ppm Sb, 30 ppm Ti, 70 ppm P 15 7 ppm blue dye — 1,4-bis[[[4-(hydroxymethyl)cyclohexyl]methyl]amino]anthraquinone

The ester exchange and polymerization of this polymer was carried out as described in Example 3. The resulting polymer was a clear "blue-white" and had an inherent viscosity of 0.624.

EXAMPLE 8

Preparation of "Blue-White" Polyester 20 145.50 g (0.75 mole) dimethyl terephthalate 70.00 g (1.12 moles) ethylene glycol 32.80 g (0.23 mole) 1,4-cyclohexanedimethanol 55 ppm Mn, 50 ppm Ti, 100 ppm P (catalysts)

7 ppm blue dye 1,4-bis[[[4-(hydroxymethyl)cyclohexyl]methyl]amino]anthraquinone 25 1 ppm red dye 1,5-bis[[[4-(hydroxymethyl)cyclohexyl]methyl]amino]anthraquinone

The ester exchange and polymerization of this polymer was carried out as described in Example 3. The resulting polymer was a clear "blue-white", and had an inherent viscosity of 0.626.

Examples of useful types of polyester, saturated and crosslinkable, are disclosed in United States Patent Specifications Nos. 2,465,319,3,668,277 and 3,560,445 and United Kingdom Patent 30 Specification No. 578,079. Among the useful polyesters are those produced from one or more diols such as 1,4-bis(hydroxymethyl)cyclohexane; ethylene glycol; 1,2-propanediol; 1,3-propanediol; 1,2-butabediol; 2,3-butanediol; 1,3-butanediol; 1,4-butanediol; 2,2-dimethyl-1,3-propanediol; 2,3-propanediol; 1,6-hexanediol; 2-ethylhexanediol; 1,2-cyclohexanediol; 1,4-cyclohexanediol; 1,2-bis(hydroxymethyl)cyclohexane; 1,3-bis-(hydroxymethyl)-cyclohexane; x,8-bis-(hydroxymethyl)-35 tricyclo[5.2.1.0]-decane wherein x represents 3, 4 or 5; and diols containing one or more oxygen atoms in the chain, e.g. diethylene glycol, triethylene glycol, dipropylene glycol or tripropylene glycol. In general, these diols contain two to 18, preferably two to 12, carbon atoms. Cycloaliphatic diols can be employed in their cis or trans configuration or as a mixture of both forms.

The acids used to form the polyesters may comprise one or more cyclic dicarboxylic acids and/or 40 acyclic dicarboxylic acids. Examples of suitable aromatic and cycloaliphatic dicarboxylic acids are terephthalic acid, isophthalic acid, hexahydroterephthalic acid, tetrahydrophthalic acid,

hexahydrophthalic acid, hexahydroisophthalic acid, as well as endomethylene- and endoethylene-tetrahydrophthalic acid, hexachloroendomethylenetetrahydrophthalic acid or tetrabromophthalic acid. The cycloaliphatic dicarboxylic acids can be employed in their trans or cis configuration or as a mixture 45 of both forms. The use of dicarboxylic acids wherein the carboxyl groups are arranged in the 1,2- or in the 1,3-position is preferred. Especially preferred are those dicarboxylic acids wherein the carboxyl groups are arranged in the 1,2-position. Of these, phthalic acid and hexahydrophthalic acid are especially preferred. In general, the cyclic dicarboxylic acids contain eight to 12 carbon atoms,

preferably eight to 10 carbon atoms. The carbocyclic dicarboxylic acids are preferred, especially the 50 monocyclic carboxylic, e.g. wherein the ring is a benzene, cyclohexane or bridged cyclohexane ring. Also useful, for example, are succinic, glutaric, adipic, suberic, sebacic, decanedicarboxylic, 2,2,4-trimethyladipic acid, maleic, fumaric, itaconic and citraconic acids. In place of the cyclic and/or acyclic dicarboxylic acids themselves, it is possible and often preferable to use a functional acid derivative thereof. For example, instead of the free dicarboxylic acids, esters thereof with lower alkanols can also 55 be employed, e.g. the dimethyl, diethyl or dipropyl ester. The anhydrides of the dicarboxylic acids can likewise be employed, e.g. phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, succinic anhydride, glutaric anhydride and maleic anhydride.

The polyesters can be produced according to conventional processes, e.g. with or without a catalyst, with or without the introduction of an inert gas stream, as solution condensation in a solvent, 60 as a melt condensation or azeotropic esterification, and at temperatures of up to 250°C., or higher, so that the water or alkanol produced by the esterification is continuously removed. The esterification takes place almost quantitatively and can be followed by measuring the hydroxyl and acid numbers. The esterification temperature may be selected so that the losses of readily volatile substances remain

5

10

15

20

25

30

35

40

45

50

55

60

GB 2 046 768 A 4

small, i.e. during at least the first period of the esterification, the process is conducted at a temperature below the boiling point of the lowest-boiling starting substance.

The unsaturated cross-linkable polyesters are the polyesterification products of one or more dihydric alcohols and one or more unsaturated dicarboxylic acids or their anhydrides, and the term 5 "polyester resin" is used herein to define the unsaturated polyester dissolved in, or cross-linked with, an 5 ethylenically unsaturated monomer. Typical is the polyesterification product of (a) 1,4-cyclohexanedimethanol and/or 2,2-dimethyl-1,3-propanediol and optionally an additional dihydric alcohol, such as ethylene glycol, and (b) maleic acid or fumaric acid or the anhydride of maleic acid, and an unsaturated hydrogenated aromatic dicarboxylic acid, which when crosslinked with an ethylenically 10 unsaturated monomer, e.g. styrene, produces a polyester resin which has, for example, high thermal 10 resistance, high heat distortion values, excellent electrical and mechanical properties, and excellent resistance to chemicals.

The unsaturated polyesters can be prepared in the presence of gelation inhibitors such as hydroquinone, which are well known in the art of polyesterification. The esterification can be carried out 15 under an inert blanket of gas such as nitrogen in a temperature range of 118—220°C. for a period of 15 6—20 hours until an acid number below 100 and preferably below 50 is obtained, based on milliequivalents of KOH necessary to neutralize 1 gram of the polyester. The resulting polyesters can be dissolved in and subsequently copolymerized with any of the well-known ethylenically unsaturated monomers used as solvents and copolymerizable monomers for polyesters. Examples of such 20 monomers include styrene, alpha-methyl styrene, vinyl toluene, divinyl benzene and chlorostyrene, as 20 well as mixtures thereof.

The unsaturated polyesters can be prepared from one or more dihydric alcohols, fumaric or maleic acid or anhydride, and up to about 60 mole percent of total acid component of o-phthalic, isophthalic or terephthalic acids or anhydrides. Preferred for the dihydric alcohol component is one or more of 25 propylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, ethylene glycol, and diethylene. 25 glycol. A preferred unsaturated polyester is prepared from propylene glycol, and as the acid component, o-phthalic anhydride and maleic anhydride in a mole ratio of from 1/2 to 2/1.

The anthraquinone dyes are used in colouring amounts, i.e. from .1.0 to 5,000 and preferably 2.0 to 1 500 parts by weight of each dye per million parts by weight of polyester.

30 The preferred coloured polyesters of this invention are linear thermoplastic polyesters having an 30 inherent viscosity of from 0.4 to 0.8, measured as previously described, the acid moiety of which comprises at least 50 mole percent terephthalic acid and the glycol moiety of which comprises at least 50 mole percent ethylene glycol or 1,4-cyclohexanedimethanol, and containing from 2.0 to 1500 parts by weight per million of one or more copolymerized dyes of the formulae

35

blue,

35

,and red

5

GB 2 046 768 A 5

HO H4C2 — N N

v~s 0

N-C2H40H

yellow

A preferred dyed polyester is prepared from dimethyl terephthalate, ethylene glycol, and from 0 to 30 mole % of 1,4-cyclohexanedimethanol based on total moles of glycol, containing from 2.0 to 1500 parts by weight of any or all of the above three dyes per one million parts by weight of polyester. 5 The following table lists dyes useful in this invention. 5

TABLE Dyes of Formula II

Example No.

Substituents on Ring A

Substituents on Ring B

10

1 — nhc%

1,4.~di-NHCH2-\ S CH20H

<•>

CH2OH

6—CH,

5 —NHCH2—\ S >

ch2oh

11

CH2OH

1

5—nhch2

ch2oh

12

1-/7V

■nhch2—^ s c^2qh 6—nhchz—{ s >—ch20h

I —S -CHgOH g —S —CH2OH

15

f —NHCH2—CH20H»4"Br 2 —NHCH2 —s CH20H 5 5-Br

.-/TV

—NHCH2—^ s ch2°h ;4-nh2 g —NHCH2—( S >—CH20H, 5-NH2

23

1-nhch2

CH20H,4-NHCH2—< S

24

f—nhch2

CH20H,4-SC2H5

25

f — NHCH2

26

j —NHCH 2

CH2OH, 4-SO2CH3

27

J,4-dl-NHCH2-< S V-CH2OH, 2-Br

28

1,4-di —NHCH2—\ s CH2OH, 2-OCeH5

29

lf4-di-NHCH2—< S V-CH2OH, 2-S02C2H5

8-nhch2—< s v-ch20h,5-nhch2—<( s

,-/7V

5_nhch2—s y?"~ CH2OH 1 8-sch3

5— nhch2—s > 8-s

'ch2oh

C Hz I

-c-ch3

ch3

5—NHCH2

CH2OH; 8~S02CH3

None

),4-di -NHCH2 CH2°H > 2,3- di-Ct

2 _NHCH2—C s V-CH20H, J-Br

I —NHCH2—S V-CH2OH

l-4dt —NHCH2—S y—CH2OH-

1 _nhch2—< s ^ ,4-C2h40ch3

"ch2oh ch90h J

j—NHCH2—/sy , 4-0C2H40C2H5

MHCH2—/ s >-CH2OH, 5-Br nhch2 nhch2

2h4ci ch2oh

^<(7>-CH2OH

> SO : 5OM/xture

-NHCH2

<i>

X

CH2OH

CHJOH -N HCH2 ^ 5

36

1—nhch2

ch20h, 2-C2H4NHCOCH3

37

1 —nhch2 \ 5 /—CH2OH, 2-CHZ-CG^5

38

1-NHCH2—< S V-CH2OH, 4-OCW2CH2Cl

39

40

41

42

43

1-NHCH2

1—N HCH2

1—nhch2

1 —NHCH2

1 -NHCH2

CH20H i4-0CH2CH2NHC0CHj

CH2OH, 4-0ch2c6h5

CH2OH ,4-NHC2H4C6Hi

CH20Ht 4-NHCOCH3

CH20H, 4-NH

CH3

q _nhch2—c s y—ch20h

8 —nhch2-—\ s • /—ch2oh

8-NHCH2—V S y—CH20H,S-0CH2CH2Cl g _NHC«2— >—CH20tf, 5-OCH2CH2NHCOC//J

8—nhch2 ( s\-ch20h , 5-0ch2CeH5

8 —NHCH2—^—-C^OH, 5-NH-C2H4CgH5

8 —NHCH2 \ S y—CH2OH; S-NH-COCH3

9-nhcHz—\ S y—ch2oh, 5-HH-

\

CH3

10

GB 2 046 768 A 10

LO

11

GB 2 046 768 A 11

Claims

1. Coloured polymeric material comprising a linear thermoplastic or unsaturated cross-linkable polyester copolymerized with a colouring compound of the formula

0

m 4P2

N -N-C2H4R

s—c a

\ s n

or

0 * v/(CH2R)n

N HCH2—< s

A

10

15

wherein R is —OH, —COOR1 or —COX wherein R1 is hydrogen or a lower alkyl radical, X is halogen, n is 1 or 2, A or B of II must contain, and A or B of I may contain, at least one additional

—NHCH2—/ s A

radical, each of rings A and B may be further substituted with 1—3 radicals selected from lower alkyl which may be substituted with lower alkoxy, phenyl, chlorine, bromine, and lower alkanoylamino; lower alkoxy which may be substituted with lower alkoxy, phenyl, chlorine, bromine, and lower alkanoylamino; chlorine; bromine; amino; lower alkylamino which may be substituted with lower alkoxy, cyclohexyl, phenyl, chlorine, bromine, and lower alkanoylamino; arylamino; arylthio; and aroylamino; wherein each aryl is 6—10 carbons; lower alkylsulphonyl; lower alkylthio; lower alkanoylamino; and cyclohexylamino.

2. Coloured polymeric material as claimed in Claim 1, wherein the colouring compound is present in a concentration of 1.0 to 5,000 parts by weight per million parts by weight of polyester, and the colouring compound has the formula

/ \

NHCH2-/ s y-CH2 OH

10

15

0 NHCH2

ch2oh

0 NHCH2-<^ s y>—CH20H

20.

or

20

HOH2C-C s Vch2nh 0

12

GB 2 046 768 A 12

30

HO H4C2 n

■N

HC c-

V

N-C2H40H

10

15

20

3. Coloured polymeric material as claimed in Claim 2, wherein the polyester is prepared from dimethyl terephthalate, ethylene glycol, and from 0 to 30 mole % of'1,4-cyclohexanedimethanol based on total moles of glycol, and the colouring compound is present in a concentration of 2.0 to 1500 parts by weight per million parts by weight of polyester.

4. Coloured polymeric material as claimed in Claim 1, wherein the polyester is unsaturated and is prepared from one or more dihydric alcohols, fumaric or maleic acid or anhydride, and up to 60 mole percent of total acid component of one or a mixture of o-phthalic, isophthalic or terephthalic acid or anhydride and the colouring compound is present in a concentration of 2.0 to 1500 parts by weight per million parts by weight of polyester.

5. Coloured polymeric material as claimed in Claim 4, wherein the dihydric alcohol is one or more of propylene glycol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, ethylene glycol, and diethylene glycol.

6. Coloured polymeric material as claimed in Claim 5, wherein the dihydric alcohol is propylene glycol and the acid component is o-phthalic anhydride and maleic anhydride in a mole ratio of from 1/2 to 2/1.

7. Coloured polymeric material as claimed in Claim 1 and substantially as hereinbefore described.

8. An article made from coloured polymeric material as claimed in Claim 1.

9. An article made from coloured polymeric material as claimed in Claim 2 or 3.

10. An article made from coloured polymeric material as claimed in Claim 4, 5 or 6.

11. Compounds of the formula

,(CH2R)n nhch2

10

15

20

wherein R is —OH, —COOR1 or —COX wherein R1 is -A or B must contain at least one additional

-H or lower alkyl, X is halogen, n is 1 or 2, either

25

-wia2—S s y group, each of rings A and B may be further substituted with 1—3 radicals selected from lower alkyl which may be substituted with lower alkoxy, phenyl, chlorine, bromine, and lower alkanoylamino; lower alkoxy which may be substituted with lower alkoxy, phenyl, chlorine, bromine, and lower alkanoylamino; chlorine; bromine; amino; lower alkylamino which may be substituted with lower alkoxy, cyclohexyl, phenyl, chlorine, bromine, and lower alkanoylamino; arylamino; arylthio; and aroylamino; wherein each aryl is 6—10 carbons; lower alkylsulphonyl; lower alkylthio; lower alkanoylamino; and cyclohexylamino.

25

30

13

GB 2 046 768 A 13

12. The compound

Examples 9 to 45.

Printad for Her Majesty's Stationery Office by the Courier Press. Leamington Spa, 1980. Published by the Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.